Third-order corrections to random-phase approximation correlation energies

Language
en
Document Type
Article
Issue Date
2012-11-06
Issue Year
2011
Authors
Heßelmann, Andreas
Editor
Abstract

Several random-phase approximation (RPA) correlation methods were compared in third order of perturbation theory. While all of the considered approaches are exact in second order of perturbation theory, it is found that their corresponding third-order correlation energy contributions strongly differ from the exact third-order correlation energy contribution due to missing interactions of the particle-particle−hole-hole type. Thus a simple correction method is derived which makes the different RPA methods also exact to third-order of perturbation theory. By studying the reaction energies of 16 chemical reactions for 21 small organic molecules and intermolecular interaction energies of 23 intermolecular complexes comprising weakly bound and hydrogen-bridged systems, it is found that the third-order correlation energy correction considerably improves the accuracy of RPA methods if compared to coupled-cluster singles doubles with perturbative triples as a reference.

Journal Title
Journal of Chemical Physics 134.20 (2011): 05.11.2012 <http://jcp.aip.org/resource/1/jcpsa6/v134/i20/p204107_s1>
Citation

Journal of Chemical Physics 134.20 (2011): 05.11.2012 http://jcp.aip.org/resource/1/jcpsa6/v134/i20/p204107_s1

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